JP4002007B2 - Gas phase reaction analyzer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas phase reaction analyzer for analyzing a reaction of a gas phase component under heating.
[0002]
[Prior art]
In recent years, it has been pointed out that harmful substances such as dioxins and environmental hormones are generated when incinerating resins and the like, and an apparatus for evaluating a reaction for detoxifying the harmful substances in order to treat the harmful substances. It is being considered. Since the harmful substance is contained in a mixture of gas phase components generated by incineration of the resin or the like, the apparatus needs to be able to analyze the reaction of the gas phase components.
[0003]
Conventionally, when analyzing a gas phase reaction, first, a solid sample is heated in a first reaction vessel to vaporize a volatile component, or the solid sample is thermally decomposed to become a reaction raw material. The gas phase component mixture is sampled and analyzed by gas chromatography or the like to determine the composition of the gas phase component mixture, and then the gas component mixture generated in the first reaction vessel is converted into the second reaction. Introduce into a vessel and further heat, or react with other gas components under heating, sample the gas phase component mixture as the reaction product obtained and analyze it by gas chromatography etc. as a reaction product The composition of the gas phase component mixture is obtained, and the composition of the reaction raw material and the reaction product is compared.
[0004]
The gas phase component generated by heating or pyrolyzing the solid sample is a multi-component mixture, and in order to generate such a multi-component mixture with high reproducibility, the temperature distribution in the container should be uniform. However, in the conventional reaction vessel, it is difficult to make the temperature distribution in the vessel uniform, and the gas phase component mixture as the reaction raw material is moved from the first reaction vessel to the second reaction vessel. When the gas phase component mixture is sampled from the first reaction vessel or the second reaction vessel and injected into the gas chromatograph, the high boiling point gas phase component is condensed and lost in the low temperature part. There's a problem. Further, when the gas phase component is analyzed as described above, there is a problem that the gas phase component mixture is adsorbed on the chemical active site because there are many chemical active sites in each reaction vessel. There is.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a gas phase reaction analyzer capable of solving such inconvenience and obtaining excellent reproducibility when analyzing the reaction of gas phase components under heating.
[0006]
[Means for Solving the Problems]
In order to achieve such an object, the gas phase reaction analysis apparatus of the present invention heats a sample in a first heating device to generate a first gas phase component mixture as a raw material for the reaction, The first gas phase component generated by analyzing the composition of the first gas phase component mixture by introducing the gas phase component mixture into the gas chromatograph and detecting it, and heating the sample in the first heating device The mixture is further heated in the second heating device as a reaction raw material to form a second gas phase component mixture as a reaction product, and the second gas phase component mixture is introduced into a gas chromatograph and detected. Analyzing the composition of the second gas phase component mixture, and comparing the compositions of the two gas phase component mixtures to produce a gas phase reaction in which the second gas phase component mixture is generated from the first gas phase component mixture. A device for analyzing the raw material of the reaction A first heating device for producing a first gas phase component mixture, and a second heating device for reacting the first gas phase component mixture to produce a second gas phase component mixture as a reaction product, And a gas chromatograph device for detecting the first gas phase component mixture and the second gas phase component mixture, wherein each heating device surrounds a chemically inert heating furnace and the periphery of the heating furnace. And a heating means provided.
[0007]
In the gas phase reaction analyzer of the present invention, first, when analyzing the composition of the first gas phase component mixture that is a raw material of the reaction, the sample is heated in the first heating device and the first gas phase component is analyzed. A composition is generated, and the composition of the first gas phase component mixture is analyzed by introducing the first gas phase component mixture into the gas chromatograph device via the second heating device and detecting the mixture. At this time, the second heating device is set to the same temperature condition as the first heating device or a temperature condition that is lower than the first heating device and does not condense the first gas phase component mixture. Thus, the first gas phase component mixture is introduced into the gas chromatograph without any change in its composition.
[0008]
Next, when analyzing the composition of the second gas phase component mixture as the reaction product, the second gas phase component mixture generated by heating the sample in the first heating device is used as the reaction raw material. In the second heating apparatus, further heating is performed in the second heating apparatus to form a second gas phase component mixture as a reaction product, and the second gas phase component mixture is introduced into the gas chromatograph apparatus. The composition of the second gas phase component mixture is analyzed by detection.
[0009]
According to the gas phase reaction analysis apparatus of the present invention, each heating device includes a heating furnace and heating means provided so as to surround the periphery of the heating furnace, so that the temperature distribution in each heating device is made uniform. In addition, it is possible to eliminate a low temperature portion where a high boiling point gas phase component may be condensed. Further, since the heating furnace is made of a chemically inert material, the chemically active point can be eliminated. As a result, according to the gas phase reaction analysis apparatus of the present invention, each gas phase component mixture can be generated with good reproducibility.
[0010]
Therefore, by examining the analysis result of the composition of both gas phase component mixtures, the reaction of the gas phase reaction that generates the second gas phase component mixture from the first gas phase component mixture in the second heating device. Analysis of the mechanism and temperature conditions suitable for performing the gas phase reaction can be performed with good reproducibility.
[0011]
In addition, as a heating apparatus provided with the said structure, the pyrolysis furnace for pyrolysis gas chromatography can be employ | adopted, for example. The gas chromatograph apparatus detects a gas component separated through a separation column using a mass spectrometer, a flame ionization detector, an atomic emission spectrometer, or the like as a detector.
[0012]
In addition, the second heating device is detachably connected between the first heating device and the detection means, thereby analyzing the composition of the first gas phase component mixture serving as a raw material for the reaction. Sometimes, the second heating device can be removed, and the first heating device and the detection means can be directly connected.
[0013]
In the gas phase reaction analysis apparatus of the present invention, the second heating device is configured to perform a plurality of reactions from the first gas phase component mixture by connecting the plurality of second heating devices in multiple stages. Then, when the second gas phase component mixture is generated, the number of the second heating devices can be increased or decreased according to the number of reactions.
[0014]
Further, in the gas phase reaction analyzing apparatus of the present invention, when the first gas phase component mixture is further heated in a second heating device to form the second gas phase component mixture, the second heating is performed. The second gas phase component mixture may be generated by reacting with other gas phase components under heating in the apparatus.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is a system configuration diagram of a gas phase reaction analysis apparatus according to the present embodiment, FIG. 2 is a system configuration diagram showing a use state of the apparatus shown in FIG. 1, and FIG. 3 is a gas phase by the apparatus shown in FIGS. It is a gas chromatogram which shows the analysis result of reaction.
[0016]
As shown in FIG. 1, the gas phase reaction analysis apparatus according to the present embodiment has a second heating device 2 connected below the first heating device 1, and a gas chromatograph device 3 connected to the second heating device 2. It has been configured.
[0017]
The heating device 1 includes a heating furnace 4a made of a chemically inert quartz tube and a heater 5a provided surrounding the heating furnace 4a. The heater 5a is controlled at a predetermined temperature condition by a control means (not shown). The heating furnace 4a is heated. The heating furnace 4a includes a sample introduction part 6a connected to the upper side, and the sample introduction part 6a is provided with a gas supply conduit 7a for supplying a carrier gas or a reaction gas into the heating furnace 4a. A discharge conduit 8a for discharging a gas phase component generated in the heating furnace 4a is provided below the heating furnace 4a.
[0018]
The heating device 2 has the same configuration as the heating device 1, and includes a heating furnace 4b, a heater 5b, a sample introduction part 6b, a gas supply conduit 7b, and a discharge conduit 8b. In the heating device 2, the sample introduction part 6 b is detachably connected to the discharge conduit 8 a of the heating device 1, and the discharge conduit 8 b of the heating device 2 is detachably connected to the sample introduction part 9 of the gas chromatograph device 3. The upper part of the sample introduction part 9 is made of heat-resistant silicone rubber, and when the discharge conduit 8b of the heating device 2 is inserted, it comes into close contact with the discharge conduit 8b and does not generate a chemically active site. ing.
[0019]
The gas chromatograph apparatus 3 includes a separation column 11 housed in a thermostatic chamber 10, and the separation column 11 has one end connected to the sample introduction unit 9 and the other end connected to the mass spectrometer 12. The thermostat 10 is heated under a predetermined temperature condition by a temperature control device (not shown).
[0020]
When performing a gas phase reaction analysis with the gas phase reaction analyzer having the above-described configuration, first, as shown in FIG. 2, the second heating device 2 is removed, and the gas chromatograph device 3 is placed below the first heating device 1. Are directly connected, a sample such as resin is accommodated in the sample cup 13 and introduced into the heating furnace 4a of the heating apparatus 1 from the sample introduction part 6a. Then, by heating the heating furnace 4a with the heater 5a under a predetermined temperature condition, the volatile component contained in the resin is vaporized, the resin is thermally decomposed, and the first vapor phase that becomes a reaction raw material. An ingredient mixture is formed.
[0021]
The first gas phase component mixture as the reaction raw material is then introduced from the discharge conduit 8a of the heating device 1 to the sample inlet 9 of the gas chromatograph device 3 by the carrier gas introduced from the gas supply conduit 7a. As a result, the first gas phase component mixture is separated by the separation column 11 of the gas chromatograph apparatus 3 and detected by the detector 12, whereby the gas chromatograph showing the composition of the first gas phase component mixture as the reaction raw material is obtained. A togram is obtained.
[0022]
Next, as shown in FIG. 1, with the second heating device 2 mounted between the first heating device 1 and the gas chromatograph device 3, the same sample as described above is accommodated in the sample cup 13. Then, the sample is introduced into the heating furnace 4a from the sample introduction part 6a of the heating apparatus 1, and a first gas phase component mixture as a reaction raw material is generated under exactly the same conditions as described above. The carrier gas introduced from 7a is introduced into the heating device 2 through the discharge conduit 8a of the heating device 1. And the heating furnace 4b is heated by the heater 5b of the heating apparatus 2 on predetermined | prescribed temperature conditions, The said 1st gaseous-phase component mixture is made to react, and the 2nd gaseous-phase component mixture as a reaction product is obtained. Alternatively, another gas phase component having reactivity is introduced from the gas supply conduit 7b and reacted with the first gas phase component mixture under heating to obtain a second gas phase component mixture as a reaction product. .
[0023]
Next, the second gas phase component mixture is guided from the discharge conduit 8 b of the heating device 2 to the sample inlet 9 of the gas chromatograph device 3 by the carrier gas introduced from the gas supply conduit 7 b of the heating device 2. As a result, a gas chromatogram showing the composition of the gas phase component of the reaction product is obtained by separating the second gas phase component mixture with the separation column 11 of the gas chromatograph apparatus 3 and detecting with the detector 12. .
[0024]
When other gas phase components having reactivity are introduced from the gas supply conduit 7b in the generation of the second gas phase component mixture as described above, the carrier gas introduced from the gas supply conduit 7a and the gas The second gas phase component mixture is guided to the sample inlet 9 of the gas chromatograph 3 by the carrier gas by the other gas phase component having the reactivity introduced from the supply conduit 7b. After the other gas phase component having the reactivity introduced from the gas supply conduit 7b is switched to the introduction of the carrier gas, the second gas phase component mixture is separated by the separation column 11 of the gas chromatograph apparatus 3. And by detecting with the detector 12, the gas chromatogram which shows the composition of the gaseous-phase component of the said reaction product is obtained.
[0025]
Therefore, by comparing the gas chromatogram showing the composition of the gas phase component as the reaction raw material obtained as described above with the gas chromatogram showing the composition of the gas phase component of the reaction product, the heating device 2 It is possible to analyze a reaction mechanism of a gas phase reaction for generating the second gas phase component mixture from the first gas phase component mixture, a temperature condition suitable for performing the gas phase reaction, and the like.
[0026]
In the present embodiment, there is only one second heating device 2, but a plurality of heating devices 2 may be connected in multiple stages according to the number of reactions.
[0027]
Further, in the present embodiment, when the composition of the first gas phase component mixture as the reaction raw material is analyzed, the first heating device 1 and the gas chromatograph device 3 are directly connected as shown in FIG. However, as shown in FIG. 1, the second heating device 2 may be mounted between the first heating device 1 and the gas chromatograph device 3. In this case, the first gas phase component mixture as the reaction raw material is introduced into the heating device 2 from the discharge conduit 8a of the heating device 1 by the carrier gas introduced from the gas supply conduit 7a, and passes through the heating device 2. The heating furnace 4b of the heating device 2 is at the same temperature condition as the heating furnace 4a of the heating device 1 or at a lower temperature than the heating furnace 4a of the heating device 1, and is introduced to the sample inlet 9 of the gas chromatograph device 3. By setting the temperature condition so that the first gas phase component mixture does not condense, the first gas phase component mixture is introduced into the gas chromatograph device 3 without any change in the heating furnace 4b of the heating device 2. can do.
[0028]
Further, in the present embodiment, when the first gas phase component mixture is generated in the first heating device 1, volatile components contained in the resin are simply vaporized by heating, or the resin is pyrolyzed. Although other gas phase components having reactivity are introduced from the gas supply conduit 7a and reacted with the gas itself or the gas phase components generated from the resin under heating, the reaction product obtained It is good also as a 1st gaseous-phase component mixture used as a reaction raw material.
[0029]
【Example】
Next, examples of gas phase reaction analysis using the gas phase reaction analysis apparatus of the present embodiment will be shown.
[0030]
In this example, a small vertical pyrolysis furnace (trade name: Model PY-2020D) manufactured by Frontier Laboratories was used as the heating devices 1 and 2. The small vertical pyrolysis furnace can perform temperature rise control from 40 ° C. to 800 ° C. at 1 ° C./min. Although the heating apparatuses 1 and 2 basically have the same configuration as described above, in this experimental example, the heating furnace 4a of the heating apparatus 1 is a quartz tube having a length of 120 mm, an inner diameter of 4 mm, and an outer diameter of 6 mm. The heating furnace 4b of the heating device 2 was a quartz tube having a length of 120 mm, an inner diameter of 10 mm, and an outer diameter of 12 mm.
[0031]
Further, the heating device 1 includes a metal needle capillary (length 50 mm, inner diameter 0.5 mm, outer diameter 0.8 mm) as the discharge conduit 8a, and the upper portion of the sample introduction part 6b of the heating device 2 is Like the sample introduction part 9 of the gas chromatograph apparatus 3, it is made of heat-resistant silicon rubber. Therefore, when the discharge conduit 8a made of the metal needle tubule of the heating device 1 is inserted into the sample introduction part 6b of the heating device 2, the heat-resistant silicone rubber is brought into close contact with the discharge conduit 8a, and the heating device 1, the heating device 2, Can be easily detached.
[0032]
In this experimental example, a capillary column for gas chromatography manufactured by Frontier Laboratories was used as the separation column 11. The capillary column used for the separation column 11 has a length of 30 m and an inner diameter of 0.25 mm, and a 5% phenylpolysiloxane stationary phase liquid is formed on the inner wall surface with a film thickness of 0.25 μm.
[0033]
In the present experimental example, a Hewlett Packard quadrupole mass spectrometer (trade name: model 5972 GC / MS) was used as the mass spectrometer 12.
[0034]
In this embodiment, first, as shown in FIG. 2, the gas chromatograph device 3 is directly connected to the lower side of the heating device 1, 0.1 mg of polycarbonate is accommodated in the sample cup 13, and the sample is introduced into the heating device 1. It installed in the part 6a. Next, the heating furnace 4a is heated to 550 ° C. by the heater 5a in a helium atmosphere introduced as a carrier gas from the gas supply conduit 7a at a flow rate of 100 ml / min, thereby heating the sample cup 13 containing the polycarbonate. By dropping into the furnace 4a and instantaneously pyrolyzing the polycarbonate, a first gas phase component mixture serving as a reaction raw material was generated.
[0035]
Next, 1/100 of the first gas phase component mixture was divided and introduced into the separation column 11 of the gas chromatograph apparatus 3 by the carrier gas introduced from the gas supply conduit 7a. The separation column 11 is accommodated in a thermostatic chamber 10 held at 40 ° C. by a temperature control device (not shown). Next, the temperature of the thermostatic chamber 10 is continuously heated from 40 ° C. to 300 ° C. at a temperature increase rate of 20 ° C./min by the temperature control device, and the first gas phase component mixture is separated by the separation column 11. The separated gas phase components were detected by the mass spectrometer 12. The obtained gas chromatogram is shown in FIG.
[0036]
From the gas chromatogram shown in FIG. 3 (a), it is clear that bisphenol A (peak A), which is suspected of acting as an environmental hormone, is produced when the polycarbonate is pyrolyzed.
[0037]
Next, as shown in FIG. 1, the heating device 2 is mounted between the heating device 1 and the gas chromatograph device 3, and the same amount of polycarbonate is accommodated in the sample cup 13. It introduced into the heating furnace 4a from the sample introduction part 6a, and the 1st gaseous-phase component mixture used as a reaction raw material on the same conditions as the above was produced | generated.
[0038]
Next, the first gas phase component mixture is introduced into the heating furnace 4b of the heating device 2 by the carrier gas introduced from the gas supply conduit 7a, and air is introduced from the gas supply conduit 7b of the heating device 2, The heating furnace 4b was heated to 850 ° C. by the heater 5b. As a result, the first gas phase component mixture is oxidized with oxygen in the air introduced from the gas supply conduit 7b of the heating device 2, thereby generating a second gas phase component mixture as a reaction product. I let you.
[0039]
Next, the separation column in which the second gas phase component mixture is accommodated in the thermostatic chamber 10 of the gas chromatograph apparatus 3 by the carrier gas introduced from the gas supply conduit 7a and the air introduced from the gas supply conduit 7b. 11 was introduced. At this time, the thermostat 10 is maintained at 40 ° C. Next, the gas introduced from the gas supply conduit 7b is switched from the air to the carrier gas helium, the air is replaced with helium, and the temperature of the thermostatic chamber 10 is changed from 40 ° C. to 20 ° C. / The gas phase component was continuously heated to 300 ° C. at a heating rate of minutes, the second gas phase component mixture was separated by the separation column 11, and each separated gas phase component was detected by the mass spectrometer 12. The obtained gas chromatogram is shown in FIG.
[0040]
In the gas chromatogram shown in FIG. 3 (b), all the peaks containing bisphenol A shown in FIG. 3 (a) disappear, and the second gas phase component mixture as the reaction product contains bisphenol A and the like. It is clear that it is not.
[0041]
Therefore, in this example, from FIGS. 3 (a) and 3 (b), a reaction product (second product) containing no bisphenol A, which is suspected to act as an environmental hormone, after pyrolyzing polycarbonate. In order to obtain a gas phase component mixture), it is possible to obtain an analysis result that an oxidation reaction with oxygen in the air may be performed at 850 ° C.
[Brief description of the drawings]
FIG. 1 is a system configuration diagram of a gas phase reaction analysis apparatus according to an embodiment.
FIG. 2 is a system configuration diagram showing a usage state of the apparatus shown in FIG.
FIG. 3 is a gas chromatogram showing analysis results of a gas phase reaction by the apparatus shown in FIGS. 1 and 2;
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... 1st heating apparatus, 2 ... 2nd heating apparatus, 3 ... Gas chromatograph apparatus .

Claims (4)

The sample is heated in the first heating device to produce a first gas phase component mixture as a raw material for the reaction, and the first gas phase component mixture is introduced into a gas chromatograph and detected. Analyzing the composition of the gas phase component mixture of 1;
The first gas phase component mixture produced by heating the sample in the first heating device is used as a raw material for the reaction, and further heated in the second heating device to produce the second gas phase component mixture as a reaction product. And analyzing the composition of the second gas phase component mixture by introducing the second gas phase component mixture into a gas chromatograph and detecting the mixture.
An apparatus for analyzing a gas phase reaction in which a second gas phase component mixture is generated from a first gas phase component mixture by comparing the compositions of both gas phase component mixtures,
A first heating device for generating a first gas phase component mixture as a raw material for the reaction;
A second heating device for reacting the first gas phase component mixture to produce a second gas phase component mixture as a reaction product;
A gas chromatograph for detecting a first gas phase component mixture and a second gas phase component mixture;
Each of the heating devices includes a chemically inert heating furnace and heating means provided so as to surround the periphery of the heating furnace.   The gas phase reaction analyzer according to claim 1, wherein the second heating device is detachably connected between the first heating device and the detection means. The gas phase reaction analysis apparatus according to claim 1 or 2, wherein the second heating device includes a plurality of the second heating devices connected in multiple stages. The first gas phase component mixture reacts with other gas phase components under heating in the second heating device to generate the second gas phase component mixture. The gas-phase reaction analyzer according to any one of claims 3 to 4.

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